Boronic Ester Based Vitrimers with Enhanced Stability via Internal Boron-Nitrogen Coordination

Boron-containing polymers have many applications resulting from their prominent properties. Organoboron species with reversible B-O bonds have been successfully employed for the fabrication of various self-healing/healable and reprocessable polymers. However, the application of the polymers containing boronic ester or boroxine linkages is limited because of their instability to water. Herein, we report the hydrolytic stability and dynamic covalent chemistry of the nitrogen-coordinating cyclic boronic diester (NCB) linkages, and a new class of vitrimers based on NCB linkages is developed through the chemical reactions of reactive hydrogen with isocyanate. Thermodynamic and kinetic studies demonstrated that NCB linkages exhibit enhanced water and heat resistance, whereas the exchange reactions between NCB linkages can take place upon heating without any catalyst. The model compounds of NCBC-X1 and NCBC-X2 containing a urethane group and urea group, respectively, also showed higher hydrolytic stability compared to that of conventional boronic esters. Polyurethane vitrimers and poly(urea-urethane) vitrimers based on NCB linkages exhibited excellent solvent resistance and mechanical properties like general thermosets, which can be repaired, reprocessed, and recycled via the transesterification of NCB linkages upon heating. Especially, vitrimers based on NCB linkages presented improved stability to water and heat compared to those through conventional boronic esters because of the existence of N -> B internal coordination. We anticipate that this work will provide a new strategy for designing the next generation of sustainable materials.